Deposition of ternary oxide films containing ruthenium and alkali earth metals

ABSTRACT

Methods and compositions for the deposition of ternary oxide films containing ruthenium and an alkali earth metal.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a continuation application of U.S.Non-provisional application Ser. No. 12/411,782, filed Mar. 26, 2009,which claims the benefit of U.S. Provisional Application No. 61/039,516,filed Mar. 26, 2008, each being incorporated herein by reference in itsentirety for all purposes.

BACKGROUND

1. Field of the Invention

This invention relates generally to compositions, methods and apparatusfor use in the manufacture of semiconductor, photovoltaic, LCD-TFT, orflat panel type devices. More specifically, the invention relates tomethods and compositions for depositing ternary oxide films on asubstrate.

2. Background of the Invention

As the design and manufacturing of semiconductor devices continues toevolve, the semiconductor industry is constantly seeking new and novelmethods of depositing films onto substrates, such that the resultingfilm will have certain sought after properties. One example of theseproperties can be found in metal electrodes to be employed in advancedCMOS technologies together with high-k dielectric films. For the nextgeneration nodes, ruthenium is considered as the best candidate forelectrode for FeRAM and DRAM applications, and potentially for MRAM. Onereason for this is that the resistibility of ruthenium is lower thaniridium and platinum. Additionally, even RuO₂ has better conductivitythan the two corresponding metal oxides in the case where a metal layeris in contact with high-k layers. Recent researches mentioned the use ofruthenium-based materials, CaRuO₃, SrRuO₃ and BaRuO₃, as an electrodefor ferroelectric applications. Ternary oxides such as ARuO₃ (A=Ca, Srand Ba) complexes show perovskite crystal structure and could be grownepitaxially on several types of insulation oxide layers. Hence, it isthought that ARuO₃ films may be suitable to be deposited on gate stackstructures. Furthermore, such films have suitable metallic conductivity.

As the size of chip becomes smaller and smaller, each layer depositedthereon should be thinner and thinner, making deposition techniques suchas chemical vapor deposition (CVD) or atomic layer deposition (ALD)desirable to deposit these layers.

A large variety of Ru precursors are available and many have beenstudied in CVD or ALD mode. However, most of them have recurrentdrawbacks: low vapor pressure (e.g. 0.25 Torr at 85° C. for Ru(EtCp)₂),high impurity contents of the obtained films (e.g. carbon and oxygen inmost of the cases), long incubation time, poor adherence, andnon-uniformity in deep trenches.

In some cases, precursors are not liquid and need to be dissolved in asolvent or mixture of solvents to allow an easy delivery of the vaporsto the reaction chamber Moreover, the solvents that are used are usuallytoxic and/or flammable and their usage brings many constraints (safetyaspects, environmental issues). Besides, the use of precursors withmelting points higher than 20° C. implies many additional constraintsduring the process deposition (heating of the delivery lines to avoidcondensation of the precursor at undesired locations) and during thetransportation.

The number of known strontium and barium precursors available for vapordeposition is low compared to ruthenium. Many strontium and bariumprecursor are solid with a high melting point (above 200° C.), and theirvapor pressure is low, which generates throughput and equipment issues.Stability may also a problem because the temperature at which theprecursor reacts with an oxidizing agent corresponds to itsdecomposition temperature.

Consequently, there exists a need for ruthenium precursors with goodreactivity and incubation time properties, which can be combined withalkali earth metal precursors which have a melting point less than about200° C. to form ternary oxide films, and which precursors may bedissolved in a suitable solvent to aid in the deposition process.

BRIEF SUMMARY

In an embodiment, a method for forming a ternary oxide film on one ormore substrates comprises providing at least one substrate disposed in areactor. A ruthenium precursor in vapor form is introduced into thereactor, where the ruthenium precursor is either ruthenium tetraoxide ora precursor with the general formula:

(L)_(m)Ru(L′)_(n)

wherein L is an unsaturated, cyclic or linear, η⁴-η⁶ type hydrocarbonligand; L′ is a linear or branched ligand, independently selected from acarbonyl, an amidinate, a β-diketonato, an alkyl, an alkoxy, hydrogen,an alkylamino; a halogen; diketimine; an enaminoketones; diazabutadiene;ethyleamine; or formamidine; and 0≦n or m≦3. An alkali earth metalprecursor in vapor form is introduced into the reactor, where the alkaliearth metal precursor has the general formula:

A(R_(x)Cp)₂R′_(y)

wherein A is either calcium, strontium, or barium; R is a linear orbranched ligand selected from a C1-C4 alkyl group, an alkoxy, a silyl,or a halogen; R′ is a linear or cyclic hydrocarbon ligand which containsN, P, or O; 0≦x≦5; and 0≦y≦2. At least part of the ruthenium and alkaliearth metal precursors are deposited to form a ternary oxide film on atleast one of the substrates.

Other embodiments of the current invention may include, withoutlimitation, one or more of the following features:

-   -   the L ligand comprises a substituted or unsubstituted ligand        selected from: butadiene; butadienyl; cyclopentadiene;        cyclopentadienyl; pentadiene; pentadienyl; hexadiene;        hexadienyl; cyclohexadiene; cyclohexadienyl; heptadiene;        heptadineyl; norbornadiene; octadiene; cylcooxtadiene; and        cyclooctadienyl;    -   the R′ ligand comprises a ligand selected from: tetrahydrofuran;        dioxane; dimethoxyethane; dimethoxyethane; and pryridine;    -   the alkali earth metal precursor has a melting point less than        about 100° C., and is preferably a liquid at about 25° C.;    -   the ruthenium precursor is selected from: ruthenium tetraoxide;        ruthenium(cyclopentadienyl)₂;        ruthenium(methylcyclopentadienyl)₂;        ruthenium(ethylcyclopentadienyl)₂;        ruthenium(isopropylcyclopentadienyl)₂;        ruthenium(CO)₃(1-methyl-1,4-cyclohexadien2);        ruthenium(2,6,6-trimethylcyclohexadienyl)₂;        ruthenium(dimethylpentadienyl)₂;        (cyclopentadienyl)ruthenium(dimethylpentadienyl);        (ethylcyclopentadienyl)ruthenium(dimethylpentadienyl);        ruthenium(toluene)(1,4-cyclohexadiene);        (cyclopentadienyl)ruthenium(amidinate); and        ruthenium(CpMe₅)(iPr-amindate).    -   the alkali earth metal precursor is selected from:        Ca(MeCp)₂(THF)_(z); Sr(MeCp)₂(THF)_(z); Ba(MeCp)₂(THF)_(z);        Ca(MeCp)₂(DME)_(z); Sr(MeCp)₂(DME)_(z); Ba(MeCp)₂(DME)_(z)        Ca(MeCp)_(z); Sr(MeCp)_(z); Ba(MeCp)_(z); Ca(EtMeCp)₂(THF)_(z);        Sr(EtCp)₂(THF)_(z); Ba(EtCp)₂(THF)_(z); Ca(EtCp)₂(DME)_(z);        Sr(EtCp)₂(DME)_(z); Ba(EtCp)₂(DME)_(z); Ca(EtCp)_(z); Sr(EtCp)₂,        Ba(EtCp)₂, Ca(iPrCp)₂(THF)_(n), Sr(iPrCp)₂(THF)_(z);        Ba(iPrCp)₂(THF)_(z); Ca(iPrCp)₂(DME)_(z); Sr(iPrCp)₂(DME)_(z);        Ba(iPrCp)₂(DME)_(z); Ca(iPrCp)₂, Sr(iPrCp)₂, Ba(iPrCp)₂,        Ca(iPr₃Cp)₂(THF)_(z); Sr(iPr₃Cp)₂(THF)_(z);        Ba(iPr₃Cp)₂(THF)_(z); Ca(iPr₃Cp)₂(DME)_(z);        Sr(iPr₃Cp)₂(DME)_(z); Ba(iPr₃Cp)₂(DME)_(z); Ca(iPr₃Cp)₂,        Sr(iPr₃Cp)₂, Ba(iPr₃Cp)₂, Ca(tBuCp)₂(THF)_(z);        Sr(tBuCp)₂(THF)_(z); Ba(tBuCp)₂(THF)_(z); Ca(tBuCp)₂(DME)_(z);        Sr(tBuCp)₂(DME)_(z); Ba(tBuCp)₂(DME)_(z); Ca(tBuCp)₂,        Sr(tBuCp)₂, Ba(tBuCp)₂, Ca(tBu₃Cp)₂(THF)_(z);        Sr(tBu₃Cp)₂(THF)_(z); Ba(tBu₃Cp)₂(THF)_(z);        Ca(tBu₃Cp)₂(DME)_(z); Sr(tBu₃Cp)₂(DME)_(z);        Ba(tBu₃Cp)₂(DME)_(z); Ca(tBu₃Cp)₂, Sr(tBu₃Cp)₂, and Ba(tBu₃Cp)₂;        and wherein 0≦z≦3;    -   the alkali earth metal precursor is initially supplied dissolved        in a solvent, and the solvent has a boiling point greater than        the melting point of the precursor;    -   the solvent has a boiling point greater than 100° C., preferably        greater than about 150° C.;    -   an oxygen containing reactant is introduced into the reactor,        and the reactant is selected from: O₂; O₃; H₂O; H₂O₂; N₂O; NO;        NO₂; and mixtures thereof;    -   the ternary oxide film is deposited through either a chemical        vapor deposition (CVD) process or through an atomic layer        deposition process;    -   the deposition process is performed at a temperature between        100° C. and about 500° C.; and    -   the ternary film is treated post deposition in an oxidizing        atmosphere, and the treatment is at a temperature higher than        that of the deposition process.

The foregoing has outlined rather broadly the features and technicaladvantages of the present invention in order that the detaileddescription of the invention that follows may be better understood.Additional features and advantages of the invention will be describedhereinafter that form the subject of the claims of the invention. Itshould be appreciated by those skilled in the art that the conceptionand the specific embodiments disclosed may be readily utilized as abasis for modifying or designing other structures for carrying out thesame purposes of the present invention. It should also be realized bythose skilled in the art that such equivalent constructions do notdepart from the spirit and scope of the invention as set forth in theappended claims.

Notation and Nomenclature

Certain terms are used throughout the following description and claimsto refer to various components and constituents. This document does notintend to distinguish between components that differ in name but notfunction.

As used herein, the term “alkyl group” refers to saturated functionalgroups containing exclusively carbon and hydrogen atoms. Further, theterm “alkyl group” may refer to linear, branched, or cyclic alkylgroups. Examples of linear alkyl groups include without limitation,methyl groups, ethyl groups, propyl groups, butyl groups, etc. Examplesof branched alkyls groups include without limitation, t-butyl. Examplesof cyclic alkyl groups include without limitation, cyclopropyl groups,cyclopentyl groups, cyclohexyl groups, etc.

As used herein, the abbreviation, “Me,” refers to a methyl group; theabbreviation, “Et,” refers to an ethyl group; the abbreviation, “t-Bu,”refers to a tertiary butyl group; and the abbreviation “Cp” refers to acyclopentadienyl group.

As used herein, the term “independently” when used in the context ofdescribing R groups should be understood to denote that the subject Rgroup is not only independently selected relative to other R groupsbearing different superscripts, but is also independently selectedrelative to any additional species of that same R group. For example inthe formula MR¹ _(x)(NR²R³)_((4-x)) where x is 2 or 3, the two or threeR¹ groups may, but need not be identical to each other or to R² or toR³. Further, it should be understood that unless specifically statedotherwise, values of R groups are independent of each other when used indifferent formulas.

DESCRIPTION OF PREFERRED EMBODIMENTS

Embodiments of the present invention provide novel methods andcompositions for the deposition of a ternary oxide film on a substrate.In general, the compositions and methods utilize a ruthenium precursorand an alkali earth metal precursor.

In some embodiments, the ruthenium precursor may have the generalformula:

where M is ruthenium; L is a substituted or unsubstituted ligandselected from butadiene, butadienyl, cyclopentadiene, cyclopentadienyl,pentadiene, pentadienyl, hexadiene, hexadienyl, cyclohexadiene,cyclohexadienyl, heptadiene, heptadineyl, norbornadiene, octadiene,cylcooxtadiene, and cyclooctadienyl; L′ is a linear or branched ligandselected from a carbonyl, a carbine, an amidinate, a β-diletonato, analkyl, an alkoxy, hydrogen, an alkylamino; a halogen; diketimine; anenaminoketones; diazabutadiene; ethyleamine; and formamidine; and 0≦n orm≦3.

In some embodiments the alkali earth metal precursor may have thegeneral formula:

wherein A is calcium, strontium, or barium; R is a linear or branchedligand selected from an alkyl group (e.g. Me, Et, nPr, IPr, nBu, tBu),an alkoxy, a silyl and a halogen; R′ is a linear or cyclic hydrocarbonligand which contains N, P or O (e.g. tetrahydrofuran, dioxane,dimethoxyethane, dimethoxyethane, pyridine); and 0≦y≦2.

In some embodiments, either the ruthenium precursor or the alkali earthmetal precursor may be dissolved in a solvent. In these embodiments, thesolvent should have a boiling point greater than 100° C., preferablygreater than about 150° C. The solvent may be distilled under an inertgas (e.g. nitrogen, argon, etc) to remove moisture and/or dissolvedoxygen. Typically, the solvent should have good affinity with theprecursors at room temperature, and have as a property a boiling pointgreater than the melting point of the precursor itself. Table 1 lists annon-exhaustive list of suitable solvents.

TABLE 1 Examples of solvents Vis- cosity Formula b.p. Density [cP] @Name (F.W.) [C.] [g/cm3] 25 C. Octane C₈H₈ (114.23) 125 0.7 0.51 TolueneC₆H₅CH₃ (92.14) 111 0.87 0.54 Xylene C₆H₄(CH₃)₂ (106.16) 138.5 0.86 0.6Mesitylene C₆H₃(CH₃)₃ (120.2) 165 0.86 0.99 Ethylbenzene C₆H₅C₂H₅(106.17) 136 0.87 0.67 Propylbenzene C₆H₅C₃H₇ (120) 159 0.86 0.81 Ethyltoluene C₆H₄(CH₃)(C₂H₅) (120.19) 160 0.86 0.63 EthylcyclohexaneC₆H₁₁C₂H₅ (112) 132 0.78 Propylcyclohexane C₆H₁₁C₃H₇ (126.1) 156.8 0.790.85 Tetrahydrofuran C₄H₈O (72.11) 66 0.89 0.46 Dioxane C₄H₈O₂ (88.11)101.1 1.03 1.2 1,2-diethoxyethane C₂H₅O(CH₂)₂OC₂H₅ 121 0.8 (118.17)Diethylene glycol CH₃O(CH₂)₂O(CH₂)₂OCH₃ 162 0.95 1.1 dimethylether(134.2) Ethoxybenzene C₆H₅OC₂H₅ (122.17) 173 0.96 1.1 Pyridine C₅H₅N(79.1) 115 0.98 0.94 Dimethyl sulfoxide (CH₃)₂S═O (78.13) 189 1.1 2.0Limonene C₁₀H₁₆ (136.24) 176 0.84 0.9

In some embodiments, the alkali earth metal precursor may be initiallydissolved in mesitylene, and the ruthenium precursor may be initiallydissolved in at least one solvent selected from: Methyl perfluoropropylether; methyl nonafluorobutyl ether; ethyl nonafluorbutyl ether;1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-Pentane;3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-trifluoromethyl-hexane;C₉F₁₂N; C₁₂F₂₇N; C₁₂F₃₃N; C₆F₁₄; C₈F₁₆; C₇F₁₆; C₅F₁₀H₂; C₄F₅H₅;1,1,2,3,3 penta fluoro propane; CF3CFHCF2CH2OCF2CFHOC3F7; andC3F7OCFHCF2CH(CH3)OCF2CFNOC4F9.

In some embodiments, the ruthenium precursor may be initially dissolvedin a mixture of methyl nonafluorobutyl ether and ethyl nonafluorbutylether.

The disclosed precursors may be deposited to form a thin film using anydeposition methods known to those of skill in the art. Examples ofsuitable deposition methods include without limitation, conventionalCVD, low pressure chemical vapor deposition (LPCVD), plasma enhancedchemical vapor depositions (PECVD), atomic layer deposition (ALD),pulsed chemical vapor deposition (P-CVD), plasma enhanced atomic layerdeposition (PE-ALD), or combinations thereof.

In an embodiment, the ruthenium and alkali earth metal precursors invapor form are introduced into a reactor. The precursors in vapor formmay be produced by vaporizing a liquid precursor solution, through aconventional vaporization step such as direct vaporization,distillation, or by bubbling an inert gas (e.g. N₂, He, Ar, etc.) intothe precursor solution and providing the inert gas plus precursormixture as a precursor vapor solution to the reactor. Bubbling with aninert gas may also remove any dissolved oxygen present in the precursorsolution.

The reactor may be any enclosure or chamber within a device in whichdeposition methods take place such as without limitation, a cold-walltype reactor, a hot-wall type reactor, a single-wafer reactor, amulti-wafer reactor, or other types of deposition systems underconditions suitable to cause the precursors to react and form thelayers.

Generally, the reactor contains one or more substrates on to which thethin films will be deposited. The one or more substrates may be anysuitable substrate used in semiconductor, photovoltaic, flat panel orLCD-TFT device manufacturing. Examples of suitable substrates includewithout limitation, silicon substrates, silica substrates, siliconnitride substrates, silicon oxy nitride substrates, tungsten substrates,or combinations thereof. Additionally, substrates comprising tungsten ornoble metals (e.g. platinum, palladium, rhodium or gold) may be used.The substrate may also have one or more layers of differing materialsalready deposited upon it.

In some embodiments, in addition to the precursor vapor solutions, areactant gas may also be introduced into the reactor. The reactant gasmay be one of oxygen, ozone, water, hydrogen peroxide, nitric oxide,nitrogen dioxide, nitrous oxide, radical species of these, as well asmixtures of any two or more of these.

The ruthenium, alkali earth metal precursors and any optional reactantsmay be introduced sequentially (as in ALD) or simultaneously (as in CVD)into the reaction chamber. Generally, when they are introducedsimultaneously, the order of their introduction is not critical (e.g.ruthenium precursor may be introduced before the alkali earth metalprecursor, and vice versa). In some embodiments, the reaction chamber ispurged with an inert gas between the introduction of the precursor andthe introduction of the reactant. In one embodiment, the reactant andthe precursors may be mixed together to form a reactant/precursormixture, and then introduced to the reactor in mixture form. In someembodiments, the reactant may be treated by a plasma, in order todecompose the reactant into its radical form. In some of theseembodiments, the plasma may generally be at a location removed from thereaction chamber, for instance, in a remotely located plasma system. Inother embodiments, the plasma may be generated or present within thereactor itself. One of skill in the art would generally recognizemethods and apparatus suitable for such plasma treatment.

In some embodiments, the temperature and the pressure within the reactorare held at conditions suitable for ALD or CVD depositions. Forinstance, the pressure in the reactor may be held between about 1 Pa and10⁵ Pa, or preferably between about 25 Pa and 10³ Pa, as required perthe deposition parameters. Likewise, the temperature in the reactor maybe held between about 100° C. and about 500° C., preferably betweenabout 150° C. and about 350° C.

In some embodiments, the precursor vapor solutions and the reaction gas,may be pulsed sequentially or simultaneously (e.g. pulsed CVD) into thereactor. Each pulse of precursor may last for a time period ranging fromabout 0.01 seconds to about 10 seconds, alternatively from about 0.3seconds to about 3 seconds, alternatively from about 0.5 seconds toabout 2 seconds. In another embodiment, the reactant gas, may also bepulsed into the reactor. In such embodiments, the pulse of each gas maylast for a time period ranging from about 0.01 seconds to about 10seconds, alternatively from about 0.3 seconds to about 3 seconds,alternatively from about 0.5 seconds to about 2 seconds.

In some embodiments, the ternary oxide film may be treated afterdeposition. The treatment may involve exposing the deposited ternaryoxide film to an oxygen containing reactant (independently selected fromoxygen, ozone, water, hydrogen peroxide, nitric oxide, nitrogen dioxide,nitrous oxide, radical species of these, as well as mixtures of any twoor more of these), where the exposure takes place at a temperaturegreater than that at which the ALD or CVD deposition process occurred.In this way, the resultant ternary film may be treated or cured toincrease the desirable properties of the resultant film.

EXAMPLES

The following non-limiting examples are provided to further illustrateembodiments of the invention. However, the examples are not intended tobe all inclusive and are not intended to limit the scope of theinventions described herein.

Ru(CO)₃(1-methyl-1,4-cyclohexadiene) is a slight yellow liquid precursorand the vapor pressure is higher than 1 Torr at 80° C. Therefore itsvapor is suitable to be introduced to a chamber/reactor by inert gasbubbling at 25° C.

Sr(iPr₃Cp)₂(THF)₂ is an off white powder and dissolves in mesitylenewith 0.1 mol/L at least. Its melting point is 94° C. and its vaporpressure is 1 Torr at 180 C. Therefore its vapor can be introduced tothe chamber by bubbling or liquid delivery.

Deposition of SRO Films by CVD:

The two precursors were used to deposit SrRuO₃ films by reaction withH₂O at 200° C. The ruthenium precursor was stored in a bubbler and itsvapors were delivered to the hot-wall reactor by a bubbling method. Thestrontium precursor was stored in a canister and heated to a temperaturewhere the compound is liquid in order to allow a bubbling deliverymethod and/or was dissolved in mesitylene and delivered to the reactionchamber by using liquid delivery system or by bubbling technique. Aninert gas, helium or nitrogen, was used as a carrier gas, as well as fordilution purpose.

Films were deposited from 200° C., at 0.5 Torr, and the deposition ratereached a plateau at 300° C. Depositions were done on TiN films as wellas on other electrode materials. The concentration of various elementsinto the SRO films was analyzed by an Auger spectrometer and SIMS, thestochiometry verified by RBS. It was proven that the carbon content inthe film was very low, and that we obtained 1:1:3 stoichiometric films.

Deposition of SRO Films by ALD:

The same precursors were used to deposit films in ALD mode at lowtemperatures (150-350° C.) using a mixture of H₂O in oxygen as aco-reactant. Films with similar characteristics as in the CVD mode wereobtained (good stochiometry, no C intrusion), as well as good stepcoverage in deep trenches.

While embodiments of this invention have been shown and described,modifications thereof can be made by one skilled in the art withoutdeparting from the spirit or teaching of this invention. The embodimentsdescribed herein are exemplary only and not limiting. Many variationsand modifications of the composition and method are possible and withinthe scope of the invention. Accordingly the scope of protection is notlimited to the embodiments described herein, but is only limited by theclaims which follow, the scope of which shall include all equivalents ofthe subject matter of the claims.

What is claimed is:
 1. A method for forming a ternary oxide film on oneor more substrates; comprising: a) providing at least one substratedisposed in a reactor; b) introducing a ruthenium precursor in vaporform into the reactor; wherein the ruthenium precursor is selected fromthe group consisting of: ruthenium tetraoxide;ruthenium(ethylcyclopentadienyl)₂;ruthenium(CO)₃(1-methyl-1,4-cyclohexadiene);(ethylcyclopentadienyl)ruthenium(dimethylpentadienyl); andruthenium(toluene)(1,4-cyclohexadiene); c) introducing an alkali earthmetal precursor in vapor form into the reactor; wherein the alkali earthmetal precursor is selected from the group consisting ofCa(iPr₃Cp)₂(THF)_(z); Sr(iPr₃Cp)₂(THF)_(z); Ba(iPr₃Cp)₂(THF)_(z);Ca(iPr₃Cp)₂(DME)_(z); Sr(iPr₃Cp)₂(DME)_(z); Ba(iPr₃Cp)₂(DME)_(z);Ca(iPr₃Cp)₂, Sr(iPr₃Cp)₂, Ba(iPr₃Cp)₂, Ca(tBu₃Cp)₂(THF)_(z);Sr(tBu₃Cp)₂(THF)_(z); Ba(tBu₃Cp)₂(THF)_(z); Ca(tBu₃Cp)₂(DME)_(z);Sr(tBu₃Cp)₂(DME)_(z); Ba(tBu₃Cp)₂(DME)_(z); Ca(tBu₃CP)₂, Sr(tBu₃Cp)₂,and Ba(tBu₃Cp)₂; and wherein 0≦z≦3 d) depositing through an atomic layerdeposition (ALD) process at least part of the ruthenium and alkali earthmetal precursors to form a ternary oxide film on at least one of thesubstrates.
 2. The method of claim 1, wherein the alkali earth metalprecursor has a melting point of less than about 100° C.
 3. The methodof claim 4, wherein the alkali earth metal precursor is a liquid atabout 25° C.
 4. The method of claim 1, wherein the alkali earth metalprecursor or the ruthenium precursor is initially supplied dissolved ina solvent, wherein the solvent has a boiling point greater than themelting point of the precursor dissolved therein.
 5. The method of claim8, where the solvent has a boiling point greater than about 100° C. 6.The method of claim 1, further comprising introducing an oxygencontaining reactant into the reactor; wherein the reactant comprises atleast one member selected from: O₂; O₃; H₂O; H₂O₂; N₂O; NO; NO₂; andmixtures thereof.
 7. The method of claim 1, further comprisingdepositing the precursors to form the ternary oxide film through eithera chemical vapor deposition (CVD) process or an atomic layer deposition(ALD) process.
 8. The method of claim 7, wherein the deposition processis performed at temperature between about 100° C. and about 500° C. 9.The method of claim 8, further comprising post-treating the ternary filmin oxidizing atmosphere, wherein the post treating occurs at atemperature higher than that of the deposition process.